Detergent compositions

ABSTRACT

Certain partial esters and partial amides of cyclic polycarboxylic acids can act as detergency builders and fabric softeners when incorporated into otherwise conventional fabric washing detergent compositions.

United States Patent [191 Barnett et al.

DETERGENT COMPOSITIONS Inventors: Philip John Barnett, Wirral; WinstonMichael Fox, West Birkenhead; Thomas McGee, Wirral, all of EnglandAssignee: Lever Brothers Company, New

York, NY.

Filed: Apr. 5, 1974 Appl. No.: 458,264

Foreign Application Priority Data Apr. 10, 1973 United Kingdom 17086/73US. Cl. 252/89; 252/544, 260/475 Int. Cl. CllD 3/20 Field Of Search252/89, 544; 260/475 R 1 Oct. 28, 1975 Primary Examiner-William E.Schulz [57] ABSTRACT Certain partial esters and partial amides of cyclicpolycarboxylic acids can act as detergency builders and fabric softenerswhen incorporated into otherwise conventional fabric washing detergentcompositions.

3 Claims, No Drawings DETERGENT COMPOSITIONS BACKGROUND OF THEINVENTION 1. Field of the Invention The present invention relates todetergent compositions adapted for use in fabric washing and whichcontain chemical compounds which act as detergency builders and fabricsofteners. The invention also relates to novel chemical compounds foruse in such detergent compositions.

2. Description of Prior Art Detergent compositions adapted for use infabric washing, particularly when such washing is to be conducted indomestic fabric washing machines, generally comprise as majoringredients detergentactive compounds and detergency builders. The mostcommonly used detergency builders are the condensed phosphates,particularly sodium tripolyphosphate, but the use of other inorganic andorganic materials, such as sodium nitrilotriacetate and sodiumethane-l-hydroxyl,l-diphosphonate, has been proposed.

It has been suggested that the use of condensed phosphates in detergentcompositions contributes to eutrophication. Considerable effort has beenexpended to find alternative materials not containing phosphorus whichcan effectively build the detergency of a detergent composition whilstnot being too expensive or having any other deleterious properties.

Another important feature of a fabric washing detergent composition isits ability to impart a soft feel to fabric articles. The majority ofconventional fabric washing detergent compositions do not alleviate theharshening of fabric articles caused by repeated washes which, in thecase of articles of clothing, may make the fabric articles lesscomfortable to have in contact with the human skin.

Various compounds have been proposed as additives in fabric washingdetergent compositions to alleviate this harshening. In general theincorporation of large amounts of softening additives in detergentcompositions is undesirable, as such additives usually do not have anyother useful function and take up space in the detergent compositionformulation, which space might otherwise be utilised for some othermulti-functional ingredient. Moreover, the degree of fabric softeningachieved by such additives to the detergent compositions is usually veryslight. Alternative proposals have involved the use of separateadditives for use during the rinsing operation, which separate additivesare intended to improve the feel of the fabric articles. More effectivesoftening is achieved by the use of rinse additives, but thisnecessitates a separate action on the part of the housewife, and the useof a second product dur' ing the washing process, and is oftenconsidered to be undesirable.

Accordingly, the use in a fabric washing detergent composition of asingle compound which acts both as an effective detergency builder andas an effective fabric softener would result in an improved detergentcomposition.

SUMMARY OF THE INVENTION By the present invention it has been found thatcertain partial esters and partial amides of cyclic polycarboxylic acidscan act as detergency builders and fabric softeners when incorporatedinto otherwise conventional fabric washing detergent compositions. Thesepartial esters and partial amides of cyclic polycarboxylic acids arehereinafter referred to as polycarboxylic acid derivatives.

According to the invention, a detergent composition comprises at leastone detergent-active compound and at least one olycarboxylic acidderivative, or a watersoluble or water-dispersible salt thereof, havingthe general formula:

(COOH),,,

wherein X is O or NH, R is a substantially linear primary or secondaryalkyl or substantially linear primary or secondary alkenyl chaincontaining on average from 14 to 20, preferably 16 to 18, carbon atoms,n is l to 4, preferably 1 or 2, m is 2 to 5, preferably 2 or 3, and thecyclic ring may be fully or partially saturated. or fully aromatic, (nm) not being greater than 6.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a preferred embodiment ofthe invention, the cyclic ring of the olycarboxylic acid derivative isfully aromatic, and the polycarboxylic acid derivative accordingly hasthe general formula:

(COOH).,.

wherein X, R, n and m have the same significance as in formula I.

It will be apparent from this disclosure to those skilled in the artthat, although the polycarboxylic acid derivatives of the invention willfunction most effectively as detergency builders and fabric softenerswhen the groups R in the above formulae are linear, nevertheless a minorproportion of slightly branched R groups may be present without asignificant drop in performance being incurred.

Polycarboxylic acid derivatives of the invention may be incorporated ina detergent composition either in the form of a partial free acid or asa water-soluble or water-dispersible salt thereof. Alkali-metal,particuarly sodium and potassium, salts are preferred, but other saltssuch as ammonium or substituted ammonium. c.g. trimethylammonium andtriethylammonium. may be used if desired. I

The polycarboxylic acid derivatives of the invention will normallycomprise from about 5 to about by weight of a detergent composition,preferably from about 15 to about 50% by weight.

Particularly preferred polycarboxylic acid derivatives of the inventionare:

0. Compounds of general formula:

(COOH) wherein X is O or NH and R is a substantially linear primary orsecondary alkyl chain containing on average from 16 to 18 carbon atoms;and b. Compounds of general formula:

(COOR):

(COOH):

wherein R is a substantially linear primary or secondary alkyl chaincontaining on average from 16 to 18 carbon atoms.

In general, the aromatic polycarboxylic acid partial esters may beprepared by reacting appropriate molar amounts of an aromaticpolycarboxylic acid, or an anhydride thereof, with a long-chainaliphatic alcohol. In some instances transesterification may berequired. The techniques associated with esterification andtransesterification are familiar to those skilled in the synthesis oforganic chemical compounds. The Examples given below illustrate indetail typical methods suitable for the preparation of the aromaticpolycarboxylic acid derivatives of the invention.

Generally speaking, the nature of the detergentactive compound orcompounds in a detergent composition of the invention is not a criticalfeature and any of the detergent-active compounds conventionally used infabric washing detergent compositions may be utilised. Those skilled inthe art of formulating detergent compositions will be familiar withthese detergentactive compounds and the various amounts and combinationsin which they may advantageously be used. The detergent-active compoundor compounds may be anionic, nonionic, amphoteric or zwitterionic incharacter.

The detergent-active compound content of the detergent composition ofthe invention will be from about 1 to about 50%, preferably from about 2to 35%, and particularly preferably from about 5 to about by weight ofthe detergent composition.

Typical anionic detergent-active compounds are water-soluble orwater-dispersible salts of various organic acids. The cations of suchsalts are generaly alkali-metals, such as sodium and, less preferably,potassium, but other cations, such as ammonium and substituted ammonium,can be used if desired. Examples of suitable organic acids are: alkylbenzene sulphonic acids, the alkyl chains of which contain from about 8to about 20 carbon atoms, such as p-dodecyl benzene sulphonic acid andlinear alkyl (C -C15) benzene sulphonic acid; the mixtures of sulphonicacids obtained by reacting linear and branched olefins, particularlylinear cracked-wax or Ziegler" alpha-olefins, containing from about 8 toabout 22 carbon atoms, with sulphur trioxide; alkyl sulphonic acidsobtained by reacting alkanes containing from about 8 to about 22 carbonatoms with sulphur dioxide/oxygen or sulphur dioxide/chlorine (followedby hydrolysis in the latter case), or by the addition of bisulphite toolefins, particularly linear cracked-wax or Ziegler alpha-olefins,containing from about 8 to about 22 carbon atoms; alkyl sulphuric acidsobtained by reacting aliphatic alcohols containing from about 8 to about22 carbon atoms with sulphur trioxide; alkyl ether sulphuric acids,obtained by reacting molar quantities of aliphatic alcohols containingfrom about 6 to about 18 carbon atoms with from about 1 to about 15moles of ethylene oxide, or a suitable mixture of ethylene oxide andpropylene oxide, and subsequently reacting the alkyoxylated alcohol withsulphur trioxide to yield the required acid; and natural or syntheticaliphatic carboxylic acids, particularly those derived from naturalsources such as tallows, coconut oil, palm oil, palm kernel oil andgroundnut oil.

Examples of suitable nonionic detergent-active compounds are:condensates of alkyl-phenols having an alkyl group (derived, forexample, from polymerised propylene, diisobutylene, octene, dodecene ornonene) containing from about 6 to 12 carbon atoms in either a straightchain or branched chain configuration, with about 5 to 25 moles ofethylene oxide per mole of alkylphenol; condensates containing fromabout 40% to about polyoxyethylene by weight and having a molecularweight of from about 5,000 to about 1 1,000 resulting from the reactionof ethylene oxide with the reaction product of ethylenediamine andexcess propylene oxide; condensates of linear or branched-chainaliphatic alcohols containing from 8 to 18 carbon atoms with ethyleneoxide, e.g. a coconut alcohol-ethylene oxide condensate containing about6 to 30 moles of ethylene oxide per mole of coconut alcohol; long-chaintertiary amine oxides corresponding to the general formula R R R N 0,wherein R 1 is an alkyl radical containing from about 8 to 18 carbonatoms and R and R 3 are each methyl, ethyl or hydroxy ethyl radicals,such as dimethyldodecylamine oxide, dimethyloctylamine oxide,dimethylhexadecylamine oxide and N-bis (hydroxyethyl) dodecylamineoxide; long-chain tertiary phosphine oxides corresponding to the generalformula RRR"P 0, wherein R is an alkyl, alkenyl or monohydroxyalkylradical containing from 10 to 18 carbon atoms and R and R" are eachalkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms,such as dimethyldodecylphosphine oxide, dimethyltetradecylphosphineoxide, ethylmethyltetradecylphosphine oxide, diethyldodecylphosphineoxide, bis (hydroxymethyl) dodecylphospine oxide, bis (2-hydroxyethyl)dodecylphosphine oxide. 2hydroxypropylmethyltetradecylphosphine oxide,dimethyloleylphosphine oxide and dimethyl-2-hydroxydodecylphosphineoxide; and dialkyl sulphoxides corresponding to the general formula RRS0, wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radicalor an alkyl or betaor gamma-monohydroxyalkyl radical containing one ortwo other oxygen atoms in the chain, the R groups containing from 10 tol8 carbon atoms and wherein R is a methyl, ethyl or alkylol radical,such as dodecyl methyl sulphoxide, tetradecyl methyl sulphoxide,3-hydroxytridecyl methyl sulphoxide, 2-

sodium-3-dodecylaminopropanesulphonate 5 hydroxydodecyl methylsulphoxide, 3-hydroxy-4- dodecyloxybutyl methyl sulphoxide, 2-hydroxy-3-decyloxypropyl methyl sulphoxide, dodecyl ethyl sulphoxide,Z-hydroxydodecyl ethyl sulphoxide and dodecyl-Z-hydroxyethyl sulphoxide.

Examples of suitable amphoteric detergent-active compounds are:derivatives of aliphatic secondary and tertiary amines, in which thealiphatic radical may be straight chain or branched and wherein one ofthe aliphatic substituents conatins from about 8 to 18 carbon atoms andone contains an anionic water solubilising group, such assodium-3-dodecylaminopropionate,

and sodium NZ-hydroxydodecyl-N-methyl-taurate.

Examples of suitable zwitterionic detergent-active compounds are:derivatives of aliphatic quaternary ammonium compounds, sulphoniumcompounds and phosphonium compounds in which the aliphatic radical maybe straight chain or branched and wherein one of the aliphaticsubstitutents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilising group, such as3-(N,N-dimethyl-N-hexadecylammonium) propane-l-sulphonate betaine,3-(N,N- dimethyl-N-hexadecyl-ammonium)-2-hydroxypropane-l-sulphonatebetaine 3-(dodecylmethyl-sulphonium) propane-l-sulphonate betaine, and3-(cetylmethylphosphonium) ethane sulphonate betaine.

Further examples of suitable detergent-active compounds commonly used inthe art are given in Surface Active Agents, Volume I by Schwartz andPerry (Interscience 1949) and Surface Active Agents, Volume II" bySchwartz, Perry and Berch (lnterscience 1958). A polycarboxylic acidderivative of the invention may be utilised as the sole detergencybuilder in a (15.1,

tergent composition, or if desired may be used in combination with oneor more known detergency builders. In particular, polycarboxylic acidderivative may be used as a partial replacement for sodiumtripolyphosphate in an otherwise conventional sodiumtripolyphosphate-containing detergent composition.

When a polycarboxylic acid derivative of the invention is used in adetergent composition in combination with other detergency builders, theamount of such other detergency builders will not be more than about20%, and preferably not more than by weight of the detergentcomposition.

Many detergency builders are known, and those skilled in the art offormulating fabric-washing detergent compositions will be familair withthese materials. Examples of known detergency builders are sodiumtripolyphosphate; sodium orthophosphate; sodium pyrophosphate; sodiumtrimetaphosphate; sodium ethanel-hydroxy-l, l-diphosphonate; sodiumcarbonate; sodium silicate; sodium citrate; sodium oxydiacetate; sodiumcarboxymethyloxysuccinate; sodium nitrilotriacetate; sodiumethylene-diaminetetraacetate; sodium salts of long-chain dicarboxylicacids, for instance straight chain (C to C alkyl or alkenyl succinicacids and malonic acids; sodium slats of alpha-sulo ROH +/EI HOOCphonated long-chain monocarboxylic acids; sodium salts of polycarboxylicacids; i.e. acids derived from the polymerisation or copolymerisation ofunsaturated carboxylic acids and unsaturated carboxy acid anhydridessuch as maleic acid, acrylic acid, itaconic acid, methacrylic acid,crotonic acid and aconitic acid, and the anhydrides of certain of theseacids, and also from the copolymerisation of the above acids andanhydrides with minor amounts of other monomers, such as ethylene, vinylmethyl ether, vinyl chloride, vinyl acetate, methyl methacrylate, methylacrylate and styrene; and modified starches such as starches oxidised,for example using sodium hypochlorite, in which some anhydroglucoseunits have been opened to give dicarboxyl units.

Furthermore, a detergent composition of the invention may contain any ofthe'conventional fabric-washing detergent composition ingredients in anyof the amountsin which such conventional ingredients are usuallyemployed therein. Examples of these additional ingredients are latherboosters, such as coconut monoethanolamide and palm kernelmonoethanolamide; lather controllers; inorganic salts such as sodiumsulphate and magnesium sulphate; oxygen-releasing bleaching agents suchas sodium perborate, sodium percarbonate, and peracid bleach precursorssuch as tetraacetyl ethylene diamine; chlorine-releasing bleachingagents such as trichloroisocyanuric acid and sodium and potassiumdichloroisocyanurates; antiredeposition agents, such as sodiumcarboxymethylcellulose; and, usually present only in minor amounts,perfumes, colourants, fluorescers, corrosion inhibitors, germicides andenzymes.

A detergent composition of the invention can be prepared using any ofthe conventional manufacturing techniques commonly used or proposed forthe preparation of detergent compositions, such as slurry-makingfollowed by spray-drying or spray-cooling, and subsequent dry-dosing ofsensitive ingredients not suitable for incorporation prior to the dryingstep. Other conventional techniques, such as noodling, granulation, andmixing by fuidisation in a fluidised bed, may be utilised as and whennecessary. Such techniques are familiar to those skilled in the art ofdetergent composition manufacture.

By using such conventional manufacturing techniques, a detergentcomposition of the invention may be prepared in any of the commonphysical forms associated with detergent compositions, such as powders,flakes, granules, noodles, cakes, bars and, in some cases, liquids.

The following Examples, in which all parts and percentages are byweight, illustrate the preparation of certain aromatic polycarboxylicacid derivatives of the invention, and their utility in detergentcompositions.

EXAMPLE I Preparation of a tallow monoester of trimellitic acid:

vvvvvvv (II) HOOC coon Continued IlOOC wherein R is a tallow group, i.e.a predominantly saturated linear hydrocarbon chain containing an averagel8 carbon atoms.

Equimolar quantities of tallow alcohol (I) and trimellitic anhydride(II) were heated together until the temperature reached about 150C. Atthis temperature the volume of the reaction mixture began to expandrapidly, and the reaction was controlled by removing the source of heat.On cooling the reaction mixture solidified and was recrystallised fromaqueous acetone. Analysis revealed that the product mixture (III) hadbeen produced.

EXAMPLE ll 25 Preparation of a further tallow monester of trimelliticEXAMPLE acid: Preparation of a C alkyl amide of trimellitic acid:

0 O CHBCOOR K 0 ROOC HOOC (Iv) (v) ROOC IRNH

2 HOOC (VIII) (IX) 0 CONHR HOOC coon coon HOOC comm COOH COOH (VII)wherein R is a substantially linear alkyl group containing an average 18carbon atoms.

Equimalor quantities of octadecyl amine (VIII) and trimellitic anhydride(IX) were mixed and dissolved in dimethylformamide at 25C. A clearsolution formed and was allowed to stand for 1 hour. A five-fold excessof water was added and the product (X) precipitated. Analysis confirmedits structure. but also showed that about 20-30% of the product was inthe form of an imide (XI).

I R (XI) HOOC l 0 EXAMPLE IV Preparation of a tallow diester ofpyromellitic acid:

ROH

K o I o HOOC (XII) (XIII) ROOC HOOC

where R is a tallow group.

EXAMPLE V Preparation of a C alkyl monoester of hemimellitic acid:

(COOH )5 ROH (X (XVI where R is a substantially linear alkyl groupcontaining on an average 18 carbon atoms, ROH being a commerciallyavailable C alcohol (trade name: Alfol).

The alcohol (XV; 1 mole) and the hemimellitic acid (XVI; 4 moles) wererefluxed in toluene in the presence of concentrated sulphuric acid,water formed during the reaction being collected in a Dean and Starkapparatus. The mole ratio of alcohol: acid was chosen to give a maximumprobability of forming the desired mono-ester; a higher proportion ofalcohol would have favoured an increased yield of (Ii-esters, etc. Therefluxing was continued until no further moisture was collected in theDean and Stark apparatus. The toluene was removed using a rotaryevaporator, and the ester, and residual unreacted alcohol, wereseparated from the unreacted acid by methanol extraction using a Soxhletextractor. The ester (XVII) was crystallised from the methanol.

EXAMPLE VI Preparation of a C alkyl monoester of mellitic acid:

(COOHh; (COOH ls (XIX) COOR (XVIII) COOR Q (xIv) COOH COOR

where R is the same as in Example V.

This was prepared by a procedure exactly analogous to that used inExample V, a I14 molar ratio of alcohol (XV) to mellitic acid (XVIII)again being used to give a high yield of the monoester (XIX).

EXAMPLES VII TO X Four detergent compositions according to the invention(Examples VII to X) and a comparative composition A were prepared havingthe following formulations:

(COOH).

(XVII) COOR m a I X A Examples IX and X had detergencies comparable to nX that of the control, and again showed superior soften- Sodium CH'U,alkyl 5 5 5 5 properties benzene sulphonate Sodium sulphonate 5 (NaOzsK) ratio 1:2) 8 X X 8 X Sfidium Sulphmc b 6 h 6 h EXAMPLES Xl TOXVlll Sodium earhoxymethy wuukm 05 (L5 "5 '5 U5 The followingcompositions according to the lnven sodium perbomm 20 20 30 30 30 tIonalso possess good detergencies and show super or gligrcseer (Photine s Swash softening characteristics when compared with 0.. 0.. 0.5 0. 0..Sodium tripulyphos conventional fabric-washing detergent compositionsphatc 10 10 40 built wholly with sodium trlpolyphosphate.

Component Parts Ex: xI Xll Xlll xIv XV xvl xvII XVlll Sodium alkylbenzene sulphonate 5 5 5 5 5 5 5 5 Sodium alkaline silicate (ma ozsioratio 12) a s 8 s 8 8 8 8 Sodium sulphate 6 6 6 6 6 6 6 6 Fluorcsccr(Photinc CBU) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Sodiumearboxymethylcellulose 0.5 0 5 0.5 0.5 0.5 0.5 0.5 0.5 Sodium pcrboratc"0 21) 20 2O 2O 20 20 Sodium tripolyphosphate 10 1O 1O 1O 1O Tallowtrimellitatc 40 3O (Ex 11) C,N alkyl amide trimellitatc (Ex lll) 4O 3OC", alkyl hcmimellitatc (Ex v) 40 C' alkyl mellitatc (Ex V1) 40 30 Inthe form of sodium salts.

What is claimed is:

Ditallow pyromellitale (Ex: 4 4O 3U l. A detergent composition comprsing I Tallow trimellitate a. from l50% by weight of an anionic, anonIonIc, an amphoteric, a zwitterionic organic detergent ac- In theform at sodium salLs. 'tive compound or a mixture thereof, and b. from5-60% by weight of a polycarboxylic acid de rivative of the followinggeneral formula Each composition was used to wash artificially soiled 40cotton test cloths in a Terg-O-Tometer apparatus, using (COXR 30l-l hardwater (CazMg ratio 2:1) at 95C for 30 minutes at a product concentrationof 0.6%, followed by a cold rinse. After drying the test cloths wereranked for softness by a panel, and were used in a photometricdetermination of the detergency produced by each composition. Thefollowing results were obtained:

(COOM),,,

l WI IX X wherein X O or NH xamp e: A Dewrgcncy. 495 60.0 622 R asubstantially linear primary or secondary alkyl Softness ranking oralkenyl chain with 14-20 carbon atoms M H, Na, K. NH trimethylortriethylammonium.

2. A composition according to claim 1, wherein n 1, R is a substantiallylinear primary or secondary alkyl chain with 16-18 carbon atoms, and m2.

3. A composition according to claim 1, wherein X 0, n 2, m 2 and R is asubstantially linear primary or secondary alkyl chain with 16-18 carbonatoms.

1. A DETERGENT COMPOSITION COMPRISING A FROM 1-50% BY WEIGHT OF ANANIONIC, A NONINIC AN AMPHPTERIC, A ZWITTERIONIC ORGAIC DETERGENTACTIVECOMPOUND OR A MIXTURE THEREOF. AND B. FROM 5-60% BY WEIGHT OF APOLYCARBOXYLIC ACID DERIVATIVE OF THE FOLLOWING GENERAL FORMULA
 2. Acomposition according to claim 1, wherein n 1, R is a substantiallylinear primary or secondary alkyl chain with 16-18 carbon atoms, and m2.
 3. A composition according to claim 1, wherein X 0, n 2, m 2 and R isa substantially linear primary or secondary alkyl chain with 16-18carbon atoms.